Correlated fine structure branching ratios arising from state-selected predissociation of ClO (A2Π3/2)

Abstract

We have extended our investigation of the v'-dependent predissociation dynamics of the ClO A(2)Pi(3/2) state using velocity-map ion imaging. Correlated fine-structure branching ratios are reported for v' = 0-5. The measured branching ratios are non-statistical and are qualitatively inconsistent with adiabatic dissociation dynamics. The coupling constants between the A(2)Pi(3/2) state and several dissociative excited state potentials have been optimized, as have the locations of the crossing points, based on comparison to previously reported v'-dependent predissociation rates. Using these optimized potentials we have modeled the branching ratios in the diabatic limit but the lack of agreement with experiments suggests the importance of exit channel coupling. Coupled channel calculations including 9 coupled potentials provide modest improvement with experiment but differences remain.